WO2008035637A1 - Milieu filtrant et son procédé de fabrication - Google Patents

Milieu filtrant et son procédé de fabrication Download PDF

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Publication number
WO2008035637A1
WO2008035637A1 PCT/JP2007/067969 JP2007067969W WO2008035637A1 WO 2008035637 A1 WO2008035637 A1 WO 2008035637A1 JP 2007067969 W JP2007067969 W JP 2007067969W WO 2008035637 A1 WO2008035637 A1 WO 2008035637A1
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WO
WIPO (PCT)
Prior art keywords
water
nonwoven fabric
thermoplastic resin
filter material
soluble thermoplastic
Prior art date
Application number
PCT/JP2007/067969
Other languages
English (en)
Japanese (ja)
Inventor
Takuya Tsujimoto
Midori Hikasa
Original Assignee
Kuraray Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co., Ltd. filed Critical Kuraray Co., Ltd.
Priority to JP2008535339A priority Critical patent/JPWO2008035637A1/ja
Priority to EP07807373A priority patent/EP2065081A4/fr
Priority to US12/442,124 priority patent/US20100072126A1/en
Publication of WO2008035637A1 publication Critical patent/WO2008035637A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/08—Special characteristics of binders

Definitions

  • the present invention relates to a filter material composed of extra-fine long fiber nonwoven fabric and a method for producing the same. More specifically, the present invention relates to a fuel filter material that has excellent durability performance, can efficiently collect fine particles in fuel, and can remove even a small amount of moisture, and a method for producing the same.
  • Filaments, non-woven fabrics, membranes, and the like have been conventionally used as filter media for removing fine particles contained in gases and liquids.
  • the membrane filter material has a uniform micropore diameter and is a force surface filtration that enables precise filtration. Therefore, the pressure loss due to dust increases rapidly, and the filter must be replaced frequently. There is a need .
  • the fiber filter material has the disadvantage that it is difficult to obtain a uniform and fine pore diameter sheet because the fiber diameter is not uniform in the fiber distribution state, but there is a lot of space in the sheet. The rise in pressure loss due to the trapped dust is gradual, and the filter has a long life, so it is widely used.
  • a filter material for example, a filter material for liquid fuel
  • fiber-based filter materials such as cellulosic fibers, spunbond nonwoven fabrics, melt blown nonwoven fabrics, and the like are used.
  • Cellulose fibers are often used as fuel filters.
  • the filter material for liquid fuel has been required to be more restrictive of soot nitrogen oxide after 1S combustion, which has traditionally been required to collect fine particles of about 10 m in addition to stability and durability.
  • liquid fuel filter materials are becoming increasingly important to improve performance, and the ability to trap microparticles is being demanded.
  • light oil used as diesel engine fuel among liquid fuels is required to remove impurities at a higher level in terms of exhaust gas regulations.
  • melt blown nonwoven fabrics make use of the large surface area due to the small fiber diameter, and are widely used as filter materials.
  • Melt blown nonwoven fabrics have low mechanical strength, especially high durability.
  • the fiber diameter of meltblown nonwoven fabrics is limited to around 2 m, and in order to capture finer dust, the density is adjusted by calendering or other means to increase the collection rate.
  • liquid permeability tends to be hindered.
  • polybutanol (hereinafter sometimes abbreviated as PVA) is a water-soluble polymer, and its ability to change the degree of water-solubility according to its basic skeleton, molecular structure, morphology, and various modifications S The power S can be known.
  • PVA polybutanol
  • Patent Document 1 In the Japanese Patent Application Laid-Open No. 2001-262456 (Patent Document 1), the present inventors manufactured a nonwoven fabric composed of composite long fibers of PVA and another thermoplastic polymer by melt spinning. We have proposed a long-fiber nonwoven fabric with an unusual cross-section or ultrafineness obtained by extracting and removing PVA from water.
  • Patent Document 2 by controlling the extraction conditions in a nonwoven fabric composed of composite long fibers similar to Patent Document 1 to leave a part of the PVA in the nonwoven fabric, There has been proposed a method for obtaining an ultra-thin fiber nonwoven fabric having excellent durability and hydrophilicity. Furthermore, Patent Document 2 also describes that the ultra-thin fiber nonwoven fabric obtained by this method is suitable as a filter material!
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2001-262456 (paragraph [0039], Example 14)
  • Patent Document 2 JP-A-2006-89851 (Claims 1, 13, and 19)
  • an object of the present invention is to provide a filter material having a high collection property and liquid permeability and a method for producing the same.
  • Another object of the present invention is to provide a filter material that suppresses the elution of chemical substances and the loss of fibers even when used for a long period of time and has excellent durability performance, and a method for producing the same. Means for solving the problem
  • the filter material of the present invention is a filter material composed of an ultra-thin fiber nonwoven fabric having an average fiber diameter of 0.05 to 1.8 ⁇ m, and has an average width of 3 to 100 ⁇ m. Extra long fiber bundles occupy the surface of the nonwoven fabric in an area ratio of 1 to 20%, and the longitudinal and lateral bows of the nonwoven fabric I.
  • the ultrafine fibers are composed of a water-insoluble thermoplastic resin (for example, a polyester resin), and the nonwoven fabric is a water-soluble thermoplastic resin (for example, an ⁇ -olefin unit having 4 or less carbon atoms and Selected from C alkyl butyl ether units
  • the at least one unit has;! ⁇ 20 mol 0/0 containing denatured poly Bulle alcohols, in particular, modified poly Bulle alcohols containing ethylene units 3 to 20 mol%) 0 - 0;! ⁇ 2 mass You may contain in the ratio of about%.
  • the nonwoven fabric may be entangled by needle punching or water jetting.
  • the filter material of the present invention may be further laminated with other woven fabric or non-woven fabric.
  • the filter material of the present invention is suitable as a liquid fuel filter material such as a diesel engine fuel filter material.
  • the water-soluble thermoplastic resin is removed from a nonwoven or non-woven web of composite long fibers composed of a water-soluble thermoplastic resin and a water-insoluble thermoplastic resin, and the average fiber diameter is 0.05. -1.
  • a method for producing a filter material in which a part of the water-soluble thermoplastic resin remains is also included.
  • the upper and lower sides of the composite long fiber nonwoven fabric may be covered with a water-soluble sheet, and the water-soluble thermoplastic resin may be continuously removed in that state. Further, the dissolution or elution treatment of the water-soluble thermoplastic resin may be started at 60 ° C. or lower, gradually increased in temperature, and finally processed at a temperature of 80 to 110 ° C. Furthermore, the dissolution or elution treatment may be performed in the presence of a surfactant (particularly a nonionic surfactant).
  • a surfactant particularly a nonionic surfactant
  • the present invention is composed of extra-fine long fibers and there are moderately long and fine fiber bundles! /. Therefore, as a filter material, high collection and liquid permeability (low liquid resistance). ). The Furthermore, even if used for a long time, the elution of chemical substances and the loss of fibers are suppressed, and the durability performance is also excellent. Therefore, it is suitable as a filter material for liquid fuel filters that require high performance, especially diesel engine fuel filters.
  • FIG. 1 is a schematic cross-sectional view showing an example of a composite fiber used for producing a fuel filter material of the present invention.
  • the filter material of the present invention is composed of an extra-fine long-fiber nonwoven fabric, and the average fiber diameter is about 0.05-1.8 mm, preferably 0.1-1.5 mm. More preferably, it is about 0.2 to m.
  • the average fiber diameter of the ultrafine fibers is larger than 1.8 m, the fiber surface area that is not sufficient for ultrafineness is reduced, and the collection efficiency of the filter is remarkably reduced.
  • the average fiber diameter is smaller than 0.05 m, processability is lowered and stable production tends to be difficult.
  • the non-woven fabric has an ultra-long fiber bundle having a predetermined width made of ultra-fine long fibers at an appropriate ratio.
  • the average width (average width of the maximum width and the minimum width in the length direction of the bundle) of this ultrafine fiber bundle is about 3 to 100 Hm, preferably 6 to 90 ⁇ m, more preferably 10 to 80 About 111 (especially 20-80 111).
  • a fiber bundle with an average width of less than 3 m behaves like a single fiber and does not significantly affect its function as a fiber bundle.
  • it is preferable that the fiber bundle having an average width of more than 100 m does not substantially exist because it reduces the porosity of the nonwoven fabric as well as lowers the trapping property as a filter.
  • the non-woven fabric contains ultrafine long fiber bundles in an appropriate ratio! That is, in the non-woven fabric, an ultra-fine fiber bundle having an average width of 3 to 100 Hm occupies the surface of the non-woven fabric in an area ratio of 1 to 20%.
  • the occupancy ratio of the ultra-fine long fiber bundle can be selected as appropriate according to the application, and may be a low ratio of about 1 to 5% with emphasis on the collection property of fine dust, but preferably 3 to 18; %, More preferably 5 to 15%.
  • Such a nonwoven fabric can improve the collection property, liquid permeability, and durability in a filter (for example, a liquid fuel filter).
  • the filter material has a large liquid resistance and low liquid permeability.
  • the area occupancy ratio of the fiber bundle exceeds 20%, the function as an ultrafine fiber is not sufficiently exhibited, and the filter material has a low collection property.
  • the ratio of the fiber bundle is measured based on the area occupancy of the nonwoven fabric surface, but the fiber bundle is usually distributed at the same ratio in the entire nonwoven fabric.
  • the occupancy ratio of the ultrafine fiber bundle is measured based on an electron micrograph of the nonwoven fabric surface.
  • a plurality of fibers not only having the above-mentioned average width are parallel or overlapped in the same direction (for example, parallel) over a length of 10 m or more.
  • the fiber group was measured as a fiber bundle.
  • the non-woven fabric is composed of long fibers! / Screw C
  • the long-fiber non-woven fabric is a dry non-woven fabric obtained by needle-punching or hydroentangling a web composed of other non-woven fabrics, for example, short fibers.
  • Productivity is extremely high compared to woven fabrics and wet nonwoven fabrics obtained by rolling and drying shortcut fibers dispersed in water.
  • the long-fiber nonwoven fabric is composed of long fibers, the fibers are removed from the nonwoven fabric, which is suitable as a filter material.
  • long-fiber non-woven fabrics are generally higher than non-woven fabrics made of short fibers and non-woven fabrics made of shortcut fibers. Suitable for
  • the nonwoven fabric Since the nonwoven fabric has moderately the fiber bundles! /, It has excellent mechanical properties, and the tensile strength (B) in the longitudinal and transverse directions (unit kgf / 5cm) is the basis weight.
  • 100 X (B) / (A) ⁇ 5 is required, preferably 100 X (B) / (A) ⁇ 10 (e.g. 100 ⁇ 100 X (8) / (8) ⁇ 10), more preferably (8) / (8) ⁇ 15 (for example, 50 ⁇ 100 X (B) / (A) ⁇ 15).
  • 100 X (B) / (A) ⁇ 5 the strength of the ultra-thin fiber non-woven fabric is insufficient, and it can function adequately (for example, the strength required for fuel filters). I ca n’t.
  • the tensile strength (B) (unit: kgf / 5 cm) and the basis weight (A) (unit: g / m 2 ) preferably satisfy 100 X (B) / (A) ⁇ 100. If 100 X (B) / (A) is too large, the flexibility of the ultra-fine long-fiber nonwoven fabric may be lowered.
  • the value of 100 X (B) / (A) can be changed depending on the average fiber diameter, spinning take-up speed, fiber entanglement and thermocompression bonding conditions.
  • the value of 100 X (B) / (A) can be increased by increasing the fiber diameter, increasing the spinning take-up speed, or strengthening the fiber entanglement and thermocompression bonding conditions.
  • the ultra-thin fiber may be composed of a water-insoluble thermoplastic resin, and a small amount of water-soluble thermoplastic resin may be contained in the nonwoven fabric.
  • a water-soluble thermoplastic resin may be attached to the surface of the fiber composed of the water-insoluble thermoplastic resin. That is, it is preferable to impart hydrophilicity or wettability to the nonwoven fabric (fiber surface) by leaving a part of the water-soluble thermoplastic resin in the nonwoven fabric.
  • the nonwoven fabric is a nonwoven fabric obtained by a method of removing the water-soluble thermoplastic resin from a nonwoven fabric or nonwoven web of composite long fibers composed of a water-soluble thermoplastic resin and a water-insoluble thermoplastic resin. Particularly preferred.
  • the initial pressure loss when used as an aqueous liquid filter, the initial pressure loss can be greatly suppressed, and in an oil-based liquid filter such as a liquid fuel filter, It is possible to effectively remove trace water components that are impure substances.
  • the water-soluble thermoplastic resin when a part of the water-soluble thermoplastic resin (particularly water-soluble thermoplastic PVA) is left, the water-soluble thermoplastic resin is more water-soluble than when the water-soluble thermoplastic resin is applied to the nonwoven fabric and dried.
  • the hydrophilic property of the hydrophilic thermoplastic resin which has a high durability, allows the water-soluble thermoplastic resin to remain in the nonwoven fabric composed of ultrafine fibers having a specific thickness. Is achieved by drying under specific conditions.
  • the ratio of the water-soluble thermoplastic resin present in the ultra-thin fiber nonwoven fabric of the present invention is 4% by mass or less (eg, 0.000;! To 4% by mass) in the nonwoven fabric, for example, 0.0. ;! ⁇ 2 wt%, preferably from 0.5 02-1 5 wt 0/0, more preferably 0. 03 ⁇ ;! mass 0/0 (in particular from 0.05 to 0 8% by weight.) approximately..
  • the proportion of the water-soluble thermoplastic resin is too large, the elution of the water-soluble thermoplastic resin becomes high during use, and the dispersion of the ultrafine fibers becomes low, so that the flexibility of the nonwoven fabric is lowered.
  • the proportion of the water-soluble thermoplastic resin is too small, the water-based component collecting ability that the hydrophilicity of the nonwoven fabric is insufficient is lowered.
  • the water-soluble thermoplastic resin remaining in the non-woven fabric can be dissolved or eluted by a hydrophilic solvent (especially water) at a temperature of 120 ° C or lower and can be melt-spun if it is solid at room temperature. If there is, it will not be specifically limited.
  • a water-soluble thermoplastic resin for example, Cellulosic resin (C-alkyl cellulose ether such as methyl cellulose, hydride
  • Hydroxy C anolenosenorerose etherol such as oral xymethinoresenorelose, force neroleki
  • Carboxy C alkyl cellulose ethers such as dimethyl cellulose), polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, poly(ethylene glycol) ethers, poly(ethylene glycol)-styrenethacrylate, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene
  • Lucylene glycol resin polyethylene oxide, polypropylene oxide, etc.
  • polybule resin polybulur pyrrolidone, polybulue
  • polyburu alcohol (PVA) and the like are excellent in terms of melt spinning stability and water absorption after being immersed in water at 80 ° C for 3 minutes.
  • PVA polyburu alcohol
  • polybulal alcohols especially water-soluble thermoplastic PVA
  • the PVA is not particularly limited as long as it can be melt-spun, and includes, in addition to homopolymers, modified PVA in which a functional group is introduced by, for example, copolymerization as a main chain or modification of a terminal or a side chain.
  • modified PVA in which a functional group is introduced by, for example, copolymerization as a main chain or modification of a terminal or a side chain.
  • Ordinary and commercially available PVA cannot be melt-spun (that is, not thermoplastic) because the melting temperature and thermal decomposition temperature are close to each other.
  • various methods are required. Ingenuity is necessary.
  • the viscosity average degree of polymerization (hereinafter simply abbreviated as polymerization degree) of a water-soluble thermoplastic resin for example, water-soluble thermoplastic PVA
  • polymerization degree is, for example, about 200 800, preferably 230 600, More preferably, it is about 250 500.
  • a polymerization degree of 1500 or more for example, a polymerization degree of about 1700 or about 2100 is common.
  • a water-soluble thermoplastic resin for example, water-soluble thermoplastic PVA having an extremely low polymerization degree (200 to 800) is used. If the degree of polymerization is too small, sufficient spinnability cannot be obtained during spinning, and as a result, a satisfactory composite continuous fiber nonwoven fabric may not be obtained. On the other hand, if the degree of polymerization is too large, the melt viscosity is too high and the polymer cannot be discharged from the spinning nozzle, and a satisfactory composite long fiber nonwoven fabric may not be obtained.
  • the degree of polymerization of the water-soluble thermoplastic resin is determined by the solvent concentration in the polymerization reaction, the polymerization rate, the polymerization rate, the polymerization temperature, and the like. To lower the polymerization degree, the solvent concentration and the polymerization rate may be increased.
  • the degree of polymerization (P) of the water-soluble thermoplastic resin is measured according to JIS-K6726.
  • the degree of polymerization of water-soluble thermoplastic PVA can be calculated from the intrinsic viscosity [7]] (dl / g) measured in water at 30 ° C after complete re-saponification and purification of water-soluble thermoplastic PVA. It is calculated by the formula.
  • Saponification degree of the water-soluble thermoplastic PVA used in the present invention for example, 90-99. 99 Mo Honoré 0 / o, preferably from 92 to 99.9 Monore 0/0, more preferably from 94 to 99.8 Monore 0 About 0 . If the degree of saponification is too small, stable composite melt spinning may not be possible due to thermal decomposition or gelation, in which the thermal stability of the water-soluble thermoplastic PVA is low. On the other hand, water-soluble thermoplastic PVA with a too high degree of saponification is difficult to produce stably. To increase the degree of saponification, increase the amount of saponification catalyst, increase the reaction temperature, and increase the reaction time.
  • the water-soluble thermoplastic PVA can be obtained by saponifying the bull ester unit of the bull ester polymer.
  • the bull compound monomers for forming the bull ester unit include: formate, acetate, propionate, valerate, caprate, laurate, stearate, benzoate, vinyl bivalinate. Nore, versatic acid bur, and the like. These bur compound monomers can be used alone or in combination of two or more.
  • water-soluble thermoplastic PVA is highly productive, and in view of this, lower aliphatic carboxylic acid bulls such as blu acetate and bull propionate are preferred.
  • the water-soluble thermoplastic resin (for example, water-soluble thermoplastic PVA, etc.) constituting the ultra-thin fiber non-woven fabric of the present invention is a modified resin (for example, modified PVA) in which a copolymer unit is introduced even if it is a homopolymer.
  • modified resin for example, modified PVA
  • the types of copolymerizable monomers in the modified PVA include, for example, ⁇ -olefins (a-C olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene).
  • ⁇ -olefins a-C olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene.
  • (meth) acrylic acid and its salts (meth) acrylic acid esters [(meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid ⁇ propyl, (meth) acrylic Acid (i) (meth) acrylic acid C alkyl esters such as mouth pills], (meth) acrylamide derivatives
  • N-C alkyl (meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide)]
  • butyl ethers [methyl vinyl
  • Hydroxyl-containing butyl ethers [Ethylene glycol butyl ether, 1,3-propandiolenolevinoleetenole, 1,4 butanediolenovininoleetenore, etc.
  • Aryl ethers [C alkylalkyl ethers such as propyl aryl ether, butyl aryl ether, hexyl aryl ether, etc.], having an oxyalkylene group
  • Monomers [Bul monomers having a polyoxy C alkylene group such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, etc.], bursilanes (bulu).
  • Burtri C alkoxysilane such as trimethoxysilane
  • a-olefins and their esterified products isopropenyl oxalate, 3-butene-1-one, 4-pentene-1-ol, 5-hexene-1-one, 7-otaten-1-one, 9-decene C-al such as 1-ol, 3-methyl- 3-butene 1-ol
  • N buramides [N burformamide, N buracetoamide, N burpyrrolidone, etc.] unsaturated carboxylic acids [fumaric acid, maleic acid, itaconic acid, citraconic acid, maleic anhydride Acid, itaconic anhydride, citraconic anhydride, etc.], monomers having sulfonic acid groups [ethylene sulfonic acid, aryl sulfonic acid , Methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc.], monomers having a thione group [vinyloxy cetyl trimethyl ammonium chloride, vinyloxy butyl trimethyl ammonium chloride, etc. Roxytetra C alkylan
  • Vinyl chloride vinyloxymethylamine, vinyloxytrimethylamine, N-acrylamidoethyltrimethylammonium, etc.
  • N-acrylamide such as N-acrylamide, N-acrylamide butyltrimethylammonium chloride, N-acrylamide tetra-C alkylammonium chloride, N-acrylamidodimethyl
  • N-acrylamide di-C-anolequinoleamine such as amamine, (meth) allyltrimethylammoni
  • Dialkylamines such as rylamin, arylylamines such as arylamine, and arylylamine.
  • copolymerizable monomers can be used alone or in combination of two or more.
  • the content of these copolymerizable monomer units is usually 20 mol% with respect to the total number of moles when the number of moles of all units constituting the modified PVA (or copolymerized PVA) is 100%. It is as follows. Further, in order to exert the merit of copolymerization, it is preferable that 0.01 mol% or more is the above copolymerized unit.
  • ⁇ -C olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene are available from the viewpoint of availability.
  • C-alkanediols such as Noleetherenoles, Ethyleneglycolenovininoleetenole, 1,3-propanediolenobine ether, 1,4 butanediol butyl ether
  • Aryl ethers such as nil ether and allyl acetate, C alkyl allyl ethers such as propyl allyl ether, butyl allyl ether and hexyl allyl ether
  • alpha-Orefuin is when ethylene is particularly a preferred also have either found that fiber properties becomes higher, preferably particularly when ethylene units are present from 3 to 20 mole 0/0, preferably Ri yo Is when using modified PVA with 5 to 18 mol% ethylene units introduced
  • water-soluble thermoplastic resin for example, water-soluble thermoplastic PVA
  • water-soluble thermoplastic PVA examples include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • a bulk polymerization method or a solution polymerization method in which polymerization is performed without solvent or in a solvent such as alcohol is usually employed.
  • alcohol used as a solvent in solution polymerization of water-soluble thermoplastic PVA include lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol.
  • Initiators used for copolymerization include ⁇ , ⁇ '-azobisisobutyronitrile, azo initiators such as 2,2'-azobis (2,4 dimethylvaleronitryl), and peroxides.
  • Known initiators such as peroxide initiators such as azolyl and ⁇ -propyl peroxycarbonate. These initiators can be used alone or in combination of two or more.
  • the polymerization temperature is not particularly limited, but a range of about 0 to 200 ° C (particularly 20 to 150 ° C) is appropriate.
  • the content of the alkali metal ion in the water-soluble thermoplastic resin (for example, water-soluble thermoplastic PVA) used in the present invention is the same as that of the water-soluble thermoplastic resin (for example, water-soluble thermoplastic PVA).
  • water-soluble thermoplastic PVA for example, in terms of sodium ion with respect to 100 parts by mass, for example, 0.00001—0.05 mass per mass, preferably 0.0001—0.03 mass per mass, more preferably about 0.0005—0.01 mass per mass. It is.
  • alkali metal ions PVA with a content of less than 0.00001 parts by mass is difficult to manufacture industrially.
  • the content of alkali metal ions is too high, the polymer decomposition, gelation and fiber breakage during composite melt spinning may not be remarkably stable.
  • alkali metal ions include potassium ions and sodium ions.
  • a method for incorporating a specific amount of alkali metal ions into the water-soluble thermoplastic PVA is not particularly limited.
  • water-soluble thermoplastic PVA include alkali metal ions contained in the PVA, for example, a method of adding an alkali metal ion-containing compound after polymerizing the PVA, and saponifying the butyl ester polymer in a solvent.
  • alkali metal ions contained in the PVA
  • saponifying the butyl ester polymer in a solvent When using an alkaline substance containing alkali metal ions as a saponification catalyst, PVA is mixed with PVA and the PVA obtained by saponification is washed with a washing solution.
  • the method S for controlling the content of alkali metal ions to be used S the latter method being preferred.
  • the content of alkali metal ions can be determined by atomic absorption method.
  • Examples of the alkaline substance used as the saponification catalyst include potassium hydroxide and sodium hydroxide.
  • the proportion (molar ratio) of the alkaline substance used in the saponification catalyst is preferably 0.004—0.5 monoreca S, and especially about 0.005 to 0.05 moles per mole of the acetate unit in polyacetate. preferable.
  • the saponification catalyst may be added all at the beginning of the saponification reaction, or may be added in the middle after adding the saponification reaction at the initial stage.
  • Examples of the solvent for the saponification reaction include alcohols such as methanol, estenoles such as methyl acetate, snoreoxides such as dimethylenolesnoreoxide, and amides such as dimethylenolenolemamide. These solvents can be used alone or in combination of two or more.
  • the alcohols are preferred instrument moisture content such as methanol Among these solvents 0. 0 01 ;! mass 0/0 (preferably 0.5 003-0. 9 mass 0/0, more preferably 0. 005- Methanol controlled to about 0.8% by mass) is more preferable.
  • the cleaning liquid examples include alcohols such as methanol, ketones such as acetone, esters such as methyl acetate and ethyl acetate, hydrocarbons such as hexane, water, and the like. German or mixed liquids are more preferred!
  • the amount of the cleaning liquid is a force set so as to satisfy the content ratio of alkali metal ions. Usually, it is preferably 300 to 10000 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the water-soluble thermoplastic PVA. Is about 500 to 5000 parts by mass.
  • the washing temperature is preferably about 5 to 80 ° C, more preferably about 20 to 70 ° C.
  • the washing time is preferably about 20 minutes to 100 hours, more preferably about 1 to 50 hours.
  • a water-soluble thermoplastic resin for example, water-soluble thermoplastic PVA
  • a plasticizer for the purpose of adjusting the melting point and melt viscosity.
  • the plasticizer diglycerin, polyglycerin alkyl monocarboxylic acid esters that can use conventionally known plasticizers, compounds obtained by adding ethylene oxide and / or propylene oxide to glycols, and the like are preferably used. Among them, compounds obtained by adding 1 to 30 mol 0/0 of ethylene oxide relative to 1 mol of sorbitol is preferred.
  • the water-insoluble thermoplastic resin constituting the ultrafine fiber is not particularly limited as long as it is not dissolved by a hydrophilic solvent (particularly water) and can be melt-spun.
  • a polyester resin Aromatic polyesters (polyalkylene acrylate resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, etc.), aliphatic polyesters (polylactic acid, polyethylene succinate, polybutylene, etc.
  • polyester resins especially polyethylene terephthalate resins, polypropylene terephthalate resins
  • water-soluble thermoplastic resins especially water-soluble thermoplastic PVA.
  • Aliphatic polyester resins such as polylactic acid), polyamide resins (especially aliphatic polyamide resins such as polyamide 6 and polyamide 66), polyolefin resins (especially polypropylene resins, polyethylene resins, etc.) Olefin resin), ethylene unit
  • water-insoluble thermoplastic resin for example, water-soluble thermoplastic PVA
  • a resin having an appropriate reactive group may be used.
  • water-soluble thermoplastic PVA has the same degree of crystallinity as water-soluble thermoplastic PVA and is excellent in spinnability, so water-insoluble thermoplastic resins are polyester resins and modified polybutyl alcohol.
  • an aromatic polyester resin may be used from the viewpoint of excellent heat resistance required as a filter material for liquid fuel.
  • aromatic polyester resins polybutylene terephthalate resins, modified poly C alkylene acrylate resins (for example,
  • Modified polyethylene terephthalate resin, modified polybutylene terephthalate resin, etc. are preferable.
  • modified poly C alkylene acrylate resins include other fragrances.
  • Poly (C) alkylene arylate copolymerized with copolymer components such as aliphatic dicarboxylic acids (eg, isophthalic acid, 5-sodiumsulfoisophthalic acid, etc.) and aliphatic dicarboxylic acids (eg, sebacic acid, adipic acid, etc.) Resin.
  • copolymer components such as aliphatic dicarboxylic acids (eg, isophthalic acid, 5-sodiumsulfoisophthalic acid, etc.) and aliphatic dicarboxylic acids (eg, sebacic acid, adipic acid, etc.) Resin.
  • the proportion of the copolymer component such as aliphatic dicarboxylic acids (eg, isophthalic acid, 5-sodiumsulfoisophthalic acid, etc.) and aliphatic dicarboxylic acids (eg, sebacic acid, adipic acid, etc.) Resin.
  • Examples of the relate resin include isophthalic acid-modified polyethylene terephthalate resin and isophthalic acid-modified polybutylene terephthalate resin.
  • the ultra-thin long fiber non-woven fabric is used as necessary within a range and a range that do not impair the object and effect of the present invention.
  • Contains additives such as stabilizers (thermal stabilizers, UV absorbers, light stabilizers, antioxidants, etc.), fine particles, colorants, antistatic agents, flame retardants, plasticizers, lubricants, crystallization rate retarders, etc. You may do it.
  • stabilizers thermal stabilizers, UV absorbers, light stabilizers, antioxidants, etc.
  • fine particles fine particles
  • colorants antistatic agents
  • flame retardants plasticizers
  • lubricants crystallization rate retarders
  • thermoplastic resin It can be added to a water-insoluble thermoplastic resin.
  • polyalcohol compounds such as dariserine and sorbitol as plasticizers, organic stabilizers such as hindered phenol as heat stabilizers, copper halide compounds such as copper iodide, and alkali metal halides such as potassium iodide.
  • the use of a compound is preferable because the melt retention stability during fiberization is improved.
  • inert fine particles such as fine particles, particularly inorganic fine particles
  • the average particle size of the fine particles is, for example, 0.0;! To 5 ⁇ m (for example, 0.01 to 1 111), preferably 0.02 to 3 111, and more preferably about 0.02 to 1 rn. is there.
  • the type of fine particles is not particularly limited, and examples thereof include a compound containing silicon (such as silicic force), metal oxide (such as titanium oxide), metal carbonate (such as calcium carbonate), and metal sulfate (such as barium sulfate). Inorganic fine particles can be mentioned.
  • the proportion of the fine particles is, for example, about 0.05 to 10% by mass, preferably about 0. These fine particles can be used alone or in combination of two or more. Of these fine particles, silicon oxide such as silica, particularly, a silica force having an average particle size of about 0.02 to 1111 is preferable.
  • Extra-fine long-fiber non-woven fabric is a solution (extraction) or elution of a water-soluble thermoplastic resin with a hydrophilic solvent from a non-woven fabric made of a composite long fiber composed of a water-soluble thermoplastic resin and a water-insoluble thermoplastic resin.
  • a composite long fiber nonwoven fabric composed of a water-soluble thermoplastic resin and a water-insoluble thermoplastic resin can be efficiently produced by a so-called spunbond nonwoven fabric production method in which melt spinning and nonwoven fabric formation are directly connected. .
  • Examples of the method for producing a spunbonded nonwoven fabric include the following methods. Ma First, a water-soluble thermoplastic resin and a water-insoluble thermoplastic resin are melted and kneaded in separate extruders, and then these molten polymer flows are respectively guided to the spinning head, merged, and the flow rate is measured. And discharging from the spinning nozzle hole. Next, after the discharged yarn is cooled by a cooling device, it is pulverized by a high-speed air stream so as to obtain a target fiber diameter using a suction device such as an air jet nozzle. After that, the nonwoven web is formed by depositing on a mobile collecting surface while opening. Finally, a composite continuous fiber nonwoven fabric can be obtained by partially thermocompressing and winding the web.
  • the cross-sectional shape (cross-sectional shape perpendicular to the length direction of the fiber) of the composite long fiber constituting the composite long-fiber nonwoven fabric is not particularly limited, and is an irregular cross-section (for example, hollow, flat, elliptical, Polygonal shape, 3 ⁇ ; 14 leaf shape, T-shape, H-shape, V-shape, dogbone (I-shape, etc.) may be used, but usually round section.
  • the inside of the cross section has a composite structure composed of a phase composed of a water-insoluble thermoplastic resin and a phase composed of a water-soluble thermoplastic resin in order to form ultrafine fibers. It is.
  • the composite long fiber has a structure in which a water-soluble thermoplastic resin and a water-insoluble thermoplastic resin can be separated in the axial direction (length direction) of the composite long fiber, that is, a water-soluble thermoplastic resin. It is necessary to have a structure in which fat is dissolved and removed continuously in the axial direction to obtain ultrafine fibers of the remaining water-insoluble thermoplastic resin. Therefore, the composite long fiber is composed of a water-soluble resin phase extending in the axial direction and a plurality of water-insoluble resin phases extending coaxially with the water-soluble resin phase. And a water-soluble thermoplastic resin for dividing the ultrafine fiber component into a plurality of components.
  • the composite cross-sectional structure of such composite long fibers includes a mandarin orange cross-sectional structure or a fan-shaped structure (that is, a phase composed of a water-insoluble thermoplastic resin and a phase composed of a water-soluble thermoplastic resin).
  • a mandarin orange cross-sectional structure or a fan-shaped structure that is, a phase composed of a water-insoluble thermoplastic resin and a phase composed of a water-soluble thermoplastic resin.
  • a laminated structure that is, a phase composed of a water-insoluble thermoplastic resin and a phase composed of a water-soluble thermoplastic resin
  • a sea-island structure that is, a sea made of a water-soluble thermoplastic resin
  • the number of island components which are ultrafine fiber forming components, can be selected from a range of 5 to about 1000 from the viewpoint of productivity. Therefore, it is preferable that the number of island components is larger. For example, 50 to 800, preferably 100 to 500, and more preferably (about 200 to 450 solids (250 to 400 solids)).
  • the ratio (mass ratio) between the water-insoluble thermoplastic resin and the water-soluble thermoplastic resin in the composite long fiber is appropriately set according to the purpose and is not particularly limited, but the water-insoluble thermoplastic resin / water-soluble Thermoplastic resin can be selected from the range of about 5/95 to 95/5, for example, 10/90 to 90/10, preferably 15/85 to 85/15, more preferably 30/70 to 85/15 ( Especially 50 / 50-80 / 20).
  • the fiberizing conditions of the composite long fibers constituting the composite long-fiber nonwoven fabric are forces that need to be appropriately set according to the combination of the polymers and the structure of the composite cross section. It is desirable to determine the fiberizing conditions while paying attention to the following points.
  • the spinneret temperature is, for example, about (Mp + 10) ° C to (Mp + 80) ° C, where Mp is the melting point of a polymer having a high melting point among the polymers constituting the composite long fiber, Preferably, it is about (Mp + 15) ° C to (Mp + 70) ° C, more preferably about (Mp + 20) ° C to (Mp + 60) ° C.
  • the shear rate ( ⁇ ) in spinning is, for example, preferably 500 to 25000 seconds (1000 to 20000 sec—more preferably ⁇ 515 or more; OOOOsec— 1 ). Draft (V) in yarn thread ⁇ Is, for example, about 50 to 2000, preferably about 100 to 1500.
  • melt viscosity be a close combination of the two types of polymers (specifically, for the two polymers constituting the composite long fiber, the conditions of the die temperature during melt spinning and the shear rate when passing through the nozzle)
  • the melt viscosity is measured for each polymer, the melt viscosities of both polymers are close to each other, for example, both polymers at a shear rate of 1000 sec_1 at the die temperature.
  • Combinations difference in melt viscosity is 2000 Boys (poise) or less (preferably within 1500 Poi's) are preferred.
  • the melting point Tm of the polymer in the present invention is a differential scanning calorimeter (DSC: for example, METTLER
  • the yarn when pulling the discharged yarn using a suction device such as an air jet nozzle, the yarn is about 500 to 6000 m / min (preferably ⁇ 1000 to 5000 m / min). It is preferable that the air is pulled and thinned by a high-speed air flow at a speed corresponding to the take-up speed.
  • the take-up conditions of the yarn by the suction device are appropriately selected according to the melt viscosity of the molten polymer discharged from the spinning nozzle hole, the discharge speed, the spinning nozzle temperature, the cooling conditions, etc. If the take-up speed is too low, Adhesion between adjacent yarns may occur due to a delay in cooling and solidification, and the orientation of the yarn does not progress crystallization, and the resulting composite nonwoven fabric tends to be a nonwoven fabric with coarse and low mechanical strength. On the other hand, if the take-up speed is too high, the yarns and thinness of the discharged yarn cannot be followed, and the yarn will be cut, making it impossible to produce a stable composite long-fiber nonwoven fabric.
  • the distance between the spinning nozzle hole and a suction device such as an air jet nozzle is preferably about 30 to 200 cm (particularly 40 to 150 cm). Yes.
  • Such an interval depends on the polymer used, the composition, and the spinning conditions described above, but if the interval is too small, fusion between adjacent yarns may occur due to a delay in cooling and solidification of the discharged yarn, In addition, the orientation of the yarn's crystallization does not progress, and the resulting composite nonwoven fabric is rough and has low mechanical strength.
  • Air jet The composite long fiber thinned by a suction device such as a nozzle is the sheet surface for collection.
  • a web is formed by being dispersed and collected so as to have a substantially uniform thickness.
  • the distance between the suction device and the collection surface is preferably about 30 to 200 cm (particularly 40 to 150 cm) from the viewpoint of productivity and fiber properties of the resulting nonwoven fabric.
  • the weight of the web is about 5 to 500 g / m 2 (preferably 10 to 400 g / m 2 , more preferably 50 to 300 g / m 2 ). Is preferable.
  • the thickness of the web-formed composite long fiber that has been thinned by suction is preferably in the range of about 0 ⁇ 2 to 8dtex (preferably 0.5 ⁇ 7 to 7dtex, more preferably;! To 6dtex) in terms of productivity. ! /
  • the water-insoluble thermoplastic resin can be made extremely fine by extracting and removing the water-soluble thermoplastic resin from the composite long-fiber nonwoven fabric with a hydrophilic solvent.
  • the hydrophilic solvent include water, alcohols (methanol, ethanol, isopropanol, butanol, etc.), ketones (acetone, etc.), ethers (dioxane, tetrahydrofuran, etc.), cellosonorebs (methinorecerosonolev, Such as ethyl acetate mouth sorb, butinorecello sonoleb), calbitonore (canolebitonore, diethyleneglyconoresimethinoreethenole, diethyleneglyconoremethyl ether, etc.).
  • These hydrophilic solvents can be used alone or in combination of two or more.
  • water, C alcohols such as ethanol
  • ketones such as acetone
  • the method of extracting a water-soluble thermoplastic resin from a composite long-fiber nonwoven fabric with a hydrophilic solvent is not particularly limited, and batch-type dyeing machines such as Sakyura, Beam, Zicker, and Wiens, and dip Conventional methods such as a method using a continuous hot water treatment facility such as a pump, a vibro washer and a relaxer, and a method of injecting a high-pressure water stream can be appropriately selected. Among these methods, a method using a continuous hot water treatment facility is preferable from the viewpoint of productivity and stability of the obtained product.
  • the extraction water may be neutral or alkaline aqueous solution or acidic aqueous solution.
  • the purpose is to maintain the processability and the form stability of the product (that is, to maintain the bundle state of the ultrafine fiber bundle).
  • a circulation type that is installed in an extraction device in advance and performs continuous lamination and peeling, or a method of laminating and peeling using a separate unwinding and winding device.
  • the material of the water-permeable sheet is preferably a hydrophilic material from the viewpoint that the hydrophilic solvent sufficiently penetrates into the composite long fiber nonwoven fabric inside the water-permeable sheet and can improve the extractability and the dispersibility of the fiber bundle. From the beginning to the end of extraction and removal of the water-soluble thermoplastic resin, it is always preferred that the upper and lower sides of the long-fiber nonwoven fabric be covered with the water-permeable sheet. It is preferable to move at the same speed.
  • the removal treatment is performed so that a part of the water-soluble thermoplastic resin remains in the nonwoven fabric.
  • the ratio of the hydrophilic solvent used for dissolving and removing the water-soluble thermoplastic resin is 100 times (mass basis) or more (for example, about 100 to 2000 times that of the composite long fiber nonwoven fabric). Preferably 200 times or more (for example, 200 to 1000 times). If the amount of the hydrophilic solvent is too small, dissolution and removal of the water-soluble thermoplastic resin may be insufficient, and the desired ultra-thin fiber nonwoven fabric may not be obtained. If extraction / removal is insufficient, a method that uses a fresh hydrophilic solvent that does not contain a water-soluble thermoplastic resin and again extracts and removes the water-soluble thermoplastic resin in a hydrophilic solvent bath is used. It is done.
  • the extraction treatment temperature may be appropriately adjusted according to the purpose and the type of solvent. For example, in the case of extraction using hot water or hot water, for example, 40 to 120 ° C, preferably 60 to 110 ° C, more preferably about 80 to 100 ° C. If the treatment temperature is too low, the extractability of the water-soluble thermoplastic resin is insufficient and the productivity is lowered. On the other hand, if the treatment temperature is too high, the dissolution time of the water-soluble thermoplastic resin becomes extremely short, and stable production in the proportion of the desired water-soluble thermoplastic resin may be difficult.
  • the water-soluble thermoplastic resin is then added to the nonwoven fabric using a method such as applying a solution containing the water-soluble thermoplastic resin.
  • a method such as applying a solution containing the water-soluble thermoplastic resin.
  • the extraction processing time can be appropriately adjusted according to the purpose, the apparatus to be used, and the processing temperature, but considering the production efficiency, stability, quality and performance of the obtained ultra-thin fiber nonwoven fabric,
  • the total time is about 10 to 200 minutes (especially 10 to 150 minutes).
  • it is 0.5 to 50 minutes (especially about 1 to 20 minutes). preferable
  • the non-woven fabric is preferably shrunk by extraction.
  • the area shrinkage rate of the nonwoven fabric is preferably, for example, about !-50% (especially 5-40%). If the area shrinkage rate is too small, no significant performance improvement can be seen, while if the area shrinkage rate is too high, stable production becomes difficult.
  • a technique for effectively expressing such contractility it is preferable to dissolve or elute a water-soluble thermoplastic resin with a hydrophilic solvent in the presence of a drug! /.
  • drugs Is not particularly limited, and may be directly applied to the composite long-fiber nonwoven fabric that may be charged in a hydrophilic solvent.
  • the concentration of the drug when introduced into the hydrophilic solvent is not particularly limited, but is, for example, about 0.01 to;!% By mass, preferably about 0.;! To 0.5% by mass, and is directly applied to the nonwoven fabric. Also when giving, you may provide so that the density
  • the drug is not particularly limited as long as it is effective for expression of contractility! /, But a surfactant is preferable because it can be easily removed from the nonwoven fabric in the subsequent washing treatment step.
  • surfactant examples include an anionic surfactant (for example, fatty acid salt, alkyl sulfate salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate).
  • anionic surfactant for example, fatty acid salt, alkyl sulfate salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate.
  • nonionic surfactants for example, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acids
  • Esters for example, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acids
  • Esters glycerin fatty acid esters, polyoxyethylene alkylamines, alkyl alcohols, etc.
  • cationic and zwitterionic surfactants eg, anolequinoleamine salts, quaternary ammonia
  • alkyl betaine such as ⁇ Min oxide
  • the extraction process is started from a temperature of 70 ° C or lower (for example, about 10 to 65 ° C), and the water temperature is gradually increased to a predetermined temperature (for example, about 80 to 120 ° C), preferably 80 to It is effective to use an operation in which the temperature is raised to about 110 ° C and extraction is performed in this temperature range for about 1 minute to 2 hours (especially 2 minutes to 1 hour).
  • the rate of gradually increasing the temperature is preferably about 0.5 to 20 ° C / min (particularly;! To 15 ° C / min).
  • a batch-type method may be used in which immersion is sequentially performed in tanks having different temperatures prepared in advance.
  • the water-soluble thermoplastic resin component shrinks when dissolved, and as a result, the dispersibility of the ultra-long fiber bundle composed of the water-insoluble thermoplastic resin that is the remaining component is improved, The trapping property of the obtained filter material is improved.
  • a preferred nonwoven fabric shrinkage in the machine direction and transverse direction is about 0.5 to 30% (particularly 2.5 to 20%).
  • various methods such as a method of injecting a high-pressure water flow, a method of passing through a flowing water bath, and a method of passing between pressure rolls can be used as methods for improving the dispersibility of the composite long fiber.
  • the method is applicable, and may be applied in combination with the method of extracting and removing the water-soluble thermoplastic resin.
  • the drying temperature after extraction of the water-soluble thermoplastic resin is, for example, 120 ° C or lower (eg, 30 to 120 ° C), preferably 115 ° C or lower (eg, 40 to; 115 ° C), more preferably about 110 ° C. or less (for example, 50 to 100 ° C.). If the drying temperature is too high, crystallization of the remaining water-soluble thermoplastic resin (especially water-soluble thermoplastic PVA) proceeds and the hydrophilic performance decreases. In addition, you may dry at room temperature.
  • the drying time can be appropriately adjusted according to the purpose, the equipment to be used, and the drying temperature. Considering production efficiency, stability, quality and performance of the obtained ultra-thin fiber nonwoven fabric, the notch In the case of processing, it is within 24 hours (for example, 1 minute to 24 hours), and in the case of continuous processing, it is within about 1 hour (for example, 1 minute to 1 hour).
  • water-soluble thermoplastic PVA and the like have biodegradability, and when activated sludge treatment or soil is buried, they are converted into water and carbon dioxide. Disassembled.
  • the activated sludge method is preferred for the treatment of waste liquid (drainage) after dissolving PVA.
  • waste liquid drainage
  • the PVA used in the present invention has a low load on the incinerator with low combustion heat, the PVA may be incinerated by drying the waste water in which the PVA is dissolved.
  • the ultrafine fiber nonwoven fabric (or ultrafine fiber nonwoven fabric web) obtained in this way uses various bonding / entanglement methods in order to maintain the form as a filter material. That power S.
  • Examples of such methods include heat embossing, calendaring, war
  • Examples include the tarjet method, the needle punch method, the ultrasonic sealing method, the through air method, the stitch bond method, the emulsion bonding method, and the powder dot bonding method.
  • the needle punch method, the water jet method, the embossing method, and the calendar method are preferred from the viewpoint of appearance and quality as a nonwoven fabric, and the dispersibility of the ultrafine fiber bundle is easy to control.
  • the water jet method is particularly preferable.
  • the time for forming the sheet is not particularly limited and may be appropriately selected as necessary.
  • the sheet may be formed before or after extraction of the water-soluble thermoplastic resin with a hydrophilic solvent.
  • conditions such as the type of oil, the shape of the needle, the needle depth, the number of punches, and the like can be appropriately selected from conventional conditions.
  • the needle shape is more efficient when the number of perbs is more effective. In the range where needle breakage does not occur, about 1 to 9 perb (especially 2 to 8 perb) is preferred. A range where the needle mark does not appear strong under such conditions is preferable.
  • the number of punches depends on the choice of needle type, oil agent, etc. From the point of homogeneity or flexibility of the nonwoven fabric, it is about 50 to 5000 punches / cm 2 (particularly 100 to 4000 punches / cm 2 ).
  • the fibers may be dispersed and entangled by a plurality of treatments.
  • the needle punch method and the water jet method are particularly preferable.
  • other bonding methods for example, a relatively low temperature of about 40 to 80 ° C
  • It may be easily bonded by heat embossing with temperature (calendar method, etc.).
  • the ultra-thin long fiber nonwoven fabric may be subjected to post-processing treatment such as electrification processing by electret processing, hydrophilization processing by plasma discharge processing or corona discharge processing, depending on the purpose.
  • the ultra-fine long-fiber non-woven fabric obtained in the present invention is laminated with other non-woven fabrics (long-fiber non-woven fabrics, short-fiber non-woven fabrics, etc.), woven fabrics (woven fabrics, knitted fabrics, etc.) and the like that are not used alone. Therefore, it can be used as a laminate. Laminate with other non-woven fabrics and woven fabrics Thus, a practical function can be further imparted depending on the application. For example, when a spunbond nonwoven fabric having a normal fiber diameter is laminated on one side of the ultra-thin fiber nonwoven fabric obtained in the present invention, the shape stability can be improved.
  • basis weight of the nonwoven fabric from the viewpoint of productivity and workability, for example, 5 to 500 g / m 2, preferred properly is about 10 to 400 g / m 2, in particular, when used as a fuel filter one , 30
  • ⁇ 300g / m 2 about is preferably! /,.
  • the air permeability is, for example, 20 ml / cm 2 'sec or less (eg, 0.1 to 20 m).
  • ⁇ / cm 2 ⁇ sec preferably 0.2 to 10 ml / cm 2 'sec, more preferably 0.3 to 8 ml / cm 2 ' sec (especially 0.5 to 5 ml / cm 2 'sec) is there.
  • the ultra-thin fiber non-woven fabric obtained in this way is excellent in trapping ability for fine dust (particles) having a large surface area, and various filters, pharmaceutical industry, electronics industry, food industry, automobile, etc. It can be used as a liquid filter in the industrial field, as a gas filter in the field of household electrical appliances, the field of cabins such as automobiles, and the field of masks.
  • the filter material of the present invention has a high moisture trapping rate due to the water-soluble thermoplastic resin remaining in the nonwoven fabric, and the gaps are also retained by moderately existing fiber bundles. Therefore, it is suitable for liquid fuel filters that require high lifespan and filter characteristics.
  • the liquid fuel filter can be used in a wide range of application fields such as the automobile field and the electronics field. In particular, in the automobile field, it can be used as a filter for gasoline fuel, diesel engine fuel, and various oils.
  • the filter of the present invention is a filter that meets this requirement.
  • a material is particularly suitable.
  • the finoleter material of the present invention has a collection efficiency of 90% or more (especially 95% or more) of JIS 8 class lO ⁇ m or more measured at 0.02% by mass in light oil.
  • PVA analysis methods were in accordance with JIS K6726 unless otherwise specified.
  • the amount of modification was determined by measurement with a 500 MHz 1H-NMR apparatus (manufactured by Nippon Denshi (JEOL), GX-500) using a modified polybule ester or modified PVA.
  • the content of alkali metal ions was determined by atomic absorption method.
  • the melting point of PVA was determined by using DSC (Mettler, TA3000), raising the temperature in nitrogen to 250 ° C at a heating rate of 10 ° C / min, cooling to room temperature, and then increasing the heating rate to 10 ° C / The temperature at the peak top of the endothermic peak indicating the melting point of PVA when the temperature was raised to 250 ° C in minutes was examined.
  • the melt spinning state was visually observed and evaluated according to the following criteria.
  • the obtained nonwoven fabric was visually observed and touched and evaluated according to the following criteria.
  • a 30 cm ⁇ 30 cm nonwoven fabric sample was immersed in 2000 ml of water in an autoclave and heat-treated at 120 ° C. for 1 hour. After the treatment, the nonwoven fabric was taken out from hot water and lightly squeezed, and the same operation was carried out by replacing the extract. The water-soluble thermoplastic PVA in the nonwoven fabric was completely extracted and removed by a total of 3 repeated treatments. The ratio of water-soluble thermoplastic PVA in the nonwoven fabric was determined from the change in mass before and after treatment. [0105] [Average fiber diameter]
  • Twenty fibers were randomly selected from an enlarged photograph of the cross section of the nonwoven fabric sample taken with a microscope at a magnification of 1000 times, their fiber diameters were measured, and the average value was taken as the average fiber diameter.
  • a magnified photograph of a nonwoven fabric sample taken at a magnification of 100x with a microscope is further magnified 10 times, and the bundle width and quantity of fibers in a bundle state are measured.
  • a bundle of fibers with a bundle width of 3 to 100 m becomes the surface area of the nonwoven fabric. The proportion occupied was calculated.
  • the measurement was performed using a porometer (manufactured by Coulter Electronics, “ co lter POROMETERI”).
  • Gas oil was passed at a pressure of 0.05 MPa, the water content in the liquid before and after passage was measured, and the removal efficiency of trace water was calculated.
  • a 50-liter pressurized reactor equipped with a stirrer, nitrogen inlet, ethylene inlet and initiator addition port was charged with 15.0 kg of butyl acetate and 16.0 kg of methanol, heated to 60 ° C, and then nitrogend for 30 minutes. The system was purged with nitrogen by publishing. Next, ethylene was introduced so that the reactor pressure was 5.5 kgf / cm 2 (5.4 ⁇ 10 5 Pa). Concentration of 2, 2'-azobis (4-methoxy-1,2,4-dimethylvaleronitrile) (AMV) dissolved in methanol as an initiator 2. Prepare an 8 g / L solution and publish with nitrogen gas to form nitrogen. Replaced.
  • AMV 2, 2'-azobis (4-methoxy-1,2,4-dimethylvaleronitrile
  • the obtained PVA was set using a twin screw extruder (manufactured by Nippon Steel Works, Ltd., 30 mm ⁇ ) at a set temperature.
  • Pellets were produced by melt extrusion at 220 ° C. and a screw speed of 200 rpm.
  • the obtained PVA was used with a twin-screw extruder (manufactured by Nippon Steel Works Co., Ltd., 30 ⁇ ⁇ ) at a set temperature of 210 ° C.
  • the pellets were produced by melt extrusion at a screw rotational speed of 200 rpm.
  • PVA PVA-1 pellets obtained in Synthesis Example 1 with an intrinsic viscosity of 0 ⁇ 7 and a melting point of 240 ° C
  • isophthalic acid-modified polyethylene terephthalate copolymerization ratio of i-PET and isophthalic acid: 6 mol%)
  • the material was discharged from the spinneret at a shear rate of 2500 sec- 1 .
  • Filaments that have been spun and fined at a take-up speed of 3000 m / min with high-speed air using an ejector located at a distance of 80 cm from the nozzle while cooling the ejected spinning filaments with cooling air at 20 ° C was collected and deposited on a collecting conveyor device rotating endlessly to form a long fiber web. In the spinning state, no yarn breakage was observed, and the cross-sectional shape was very good.
  • Fig. 1 shows a cross-sectional view (cross-sectional view perpendicular to the length direction) of the obtained composite long fiber.
  • the cross-sectional structure of the fiber is a sea-island type (300 islands) consisting of a sea phase 1 composed of water-soluble thermoplastic polymer PVA and an island phase 2 composed of isophthalanol-modified polyethylene terephthalate.
  • this web is passed between a concavo-convex pattern embossing roll heated to 60 ° C and a flat roll under a linear pressure of 50 kgf / cm (490 N / cm) and subjected to partial thermocompression bonding.
  • the sea-island type 300 islands with a basis weight of 114 g / m 2 composed of long fibers with a single fiber fineness of 2.3 dtex )
  • a composite long fiber nonwoven fabric was obtained.
  • the obtained nonwoven fabric was homogeneous and extremely good.
  • the production conditions for the composite long-fiber nonwoven fabric are shown in Table 2.
  • the PVA component was extracted using a continuous multi-stage washing tank (dip-and-two-pipe system, water bath 400 L / tank). There are 6 washing tanks, and each bath temperature is set to 60 ° C ⁇ 70 ° C ⁇ 80 ° C ⁇ 90 ° C ⁇ 95 ° C ⁇ 95 ° C.
  • Nonionic surfactant manufactured by Meisei Chemical Co., Ltd., “UNICALET 1 221” was added at a concentration of 3 g / liter with respect to water.
  • the extraction treatment was performed using a polyamide mesh (PA mesh, 200 mesh) as the water-permeable sheet, with the composite long fiber nonwoven fabric sandwiched by water-permeable sheets from both sides (top and bottom), and a two-pipe pressure.
  • lMPa passed continuously at a speed of 1 m / min (residence time in each tank 1 min).
  • the long-fiber nonwoven fabric is connected.
  • it was dried with hot air at 110 ° C. for 3 minutes and peeled off from the polyamide mesh to obtain a filter material composed of an ultra-thin fiber nonwoven fabric of isophthalic acid-modified polyethylene terephthalate.
  • the percentage of PVA in the nonwoven fabric after extraction and removal was 0.05%.
  • Example 2 Using the water-insoluble polymer and PVA shown in Table 2 and adopting the spinneret and spinning conditions shown in Table 2 and adjusting the distance between the nozzle ejectors and the line net speed as appropriate, the same conditions as in Example 1 A composite long fiber nonwoven fabric was obtained below. Table 2 shows the spinning state. About the obtained composite long fiber nonwoven fabric, the PVA component was extracted using a continuous multi-stage washing tank in the same manner as in Example 1, and dried with hot air at 110 ° C for 3 minutes to constitute the desired ultrafine fiber nonwoven fabric. The obtained filter material was obtained. Even in these filter materials, the ultrafine fibers were made up of a nonwoven fabric in a sufficiently dispersed state. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • Example 2 After the production of the composite long fiber under the same conditions as in Example 1, a water jet (nozzle diameter 0 ⁇ lmm, pitch 0.6 mm, nozzle plates arranged in 3 rows, Ultrathin filaments under exactly the same conditions as in Example 1 except that sheeting with water pressure 4013 ⁇ 4 £ / «11 2 — 6013 ⁇ 4 £ / « 11 2 — 8013 ⁇ 4 £ / «11 2 , nonwoven fabric passing speed 5 m / min) was applied. A filter material composed of fiber nonwoven fabric was obtained. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • Example 10 After producing composite long fibers and forming a sheet by needle punch under the same conditions as in Example 1, as a water-permeable sheet, PET homo SB (polyethylene terephthalate non-woven fabric containing styrene butadiene rubber, manufactured by Unitica Co., Ltd., PVA extraction was performed in the same manner as in Example 1 except that “90153WSO” and a basis weight of 15 g / m 2 ) were used, and a filter material composed of ultra-thin fiber nonwoven fabric was obtained. Table 3 shows the evaluation results of various physical properties of the obtained filter material. [0128]
  • PET homo SB polyethylene terephthalate non-woven fabric containing styrene butadiene rubber, manufactured by Unitica Co., Ltd.
  • PVA extraction was performed in the same manner as in Example 1 except that “90153WSO” and a basis weight of 15 g / m 2 ) were used, and a filter material composed of ultra-thin fiber nonwoven fabric was obtained.
  • Example 3 After producing composite long fibers and forming a sheet by needle punch under the same conditions as in Example 1, except using cotton cloth (“5088E (white cedar)” manufactured by Yamamiki Planning Co., Ltd.) as a water-permeable sheet Was extracted with PVA in the same manner as in Example 1 to obtain a filter material composed of extra-fine long-fiber nonwoven fabric.
  • Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • Example 2 After manufacturing the composite long fiber and forming a sheet by needle punching under the same conditions as in Example 1, all the bath temperatures of the continuous multi-stage washing tank were set to 95 ° C, and the PVA component was extracted. A filter material composed of extra-fine long-fiber nonwoven fabric was obtained. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • Example 2 After producing composite long fibers and forming a sheet with a needle punch under the same conditions as in Example 1, PVA extraction was performed in the same manner as in Example 1 except that a nonionic surfactant was not added. The obtained filter material was obtained. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • PVA extraction is performed in the same manner as in Example 1 except that the production of composite long fibers and sheeting by needle punching are performed under the same conditions as in Example 1, and then the residence time in each layer in the continuous multistage washing tank is set to 2 minutes. And the filter material comprised with the ultra-fine long fiber nonwoven fabric was obtained. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • PET homo SB polyethylene terephthalate non-woven fabric containing styrene butadiene rubber, manufactured by Unitica Co., Ltd., 90153WSO ”, with a basis weight of 15 g / m 2
  • PVA extraction was performed to obtain a filter material composed of extra-fine long-fiber nonwoven fabric. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • Example 2 After producing composite long fibers and forming a sheet with a needle punch under the same conditions as in Example 1, the residence time in each layer in the continuous multi-stage washing tank without using a water-permeable sheet was set to 5 minutes. PVA extraction was performed in the same manner as in Example 1 to obtain a filter material composed of extra-fine long-fiber nonwoven fabric. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • PET polyethylene terephthalate
  • a spin pack at 280 ° C, nozzle diameter 0.35mm x 1008 holes
  • discharged from the spinneret at a discharge rate of 620 g / min and a shear rate of 3000 sec- 1 .
  • the discharged spinning filaments are cooled with 20 ° C cooling air, the filaments are opened and finely drawn at a take-up speed of 4000 m / min with high-speed air using an ejector located at a distance of 80 cm from the nozzle.
  • the group was collected and deposited on an endlessly rotating collection conveyor device to form a long fiber nonwoven fabric composed of polyethylene terephthalate.
  • the uneven embossing roll and the flat roll were heated to 230 ° C.
  • the fiber was passed under a linear pressure of 50 kgf / cm and subjected to partial thermocompression bonding with an emboss to obtain a long fiber nonwoven fabric having a basis weight of 65 g / m 2 composed of long fibers having a single fiber fineness of 16.5 m.
  • Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • Polyethylene terephthalate with a melt flow rate (MFR) of 400 g / 10 min was melt-kneaded at 280 ° C using a melt extruder, the molten polymer stream was guided to a melt blow die head, measured with a gear pump, and a diameter of 0.3 mm ⁇ Holes are discharged from a melt blown nozzle arranged in a row at a pitch of 0.75 mm, and simultaneously the hot air of 240 ° C is sprayed onto this resin to collect the discharged fiber on a molding conveyor, and the basis weight is 80 g / m 2 .
  • a PET ultrafine fiber nonwoven fabric was obtained. Table 3 shows the evaluation results of various physical properties of the obtained filter material.
  • the ejected spinning filaments were cooled with 20 ° C cooling air, they were pulled and thinned at a take-up speed of 3000 m / min with high-speed air by an ejector located at a distance of 80 cm from the nozzle.
  • the filament group was collected and deposited on an endless rotating collecting device to form a long fiber web.
  • this web is passed between a concavo-convex pattern embossing roll heated to 180 ° C and a flat roll under a linear pressure of 50 kgf / cm (490 N / cm), and the embossed part is thermocompression bonded.
  • a 16-segment composite long-fiber nonwoven fabric having a basis weight of 119 g / m 2 made of long fibers having a single fiber fineness of 3.2 ⁇ 2 dtex was obtained.
  • the ultrafine fibers with a small occupation ratio of the ultrafine fiber bundle are almost completely dispersed, and the obtained filter material is a filter material for fuel with a very low air permeability.
  • the liquid permeability was not sufficient.
  • the nonwoven fabric of Comparative Example 3 was only obtained as a fuel filter material with a large fiber diameter and inferior collection efficiency.
  • the nonwoven fabric of Comparative Example 4 was not sufficiently durable as a fuel filter material with low tensile strength.
  • the nonwoven fabric of Comparative Example 5 is not suitable as a filter material for fuel because the fiber bundle with a large fiber diameter is hardly separated, so the tensile strength is low, the tensile strength is low, and the collection efficiency is not sufficient. It is.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Filtering Materials (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

L'invention concerne un milieu filtrant composé d'un non-tissé de fibres de filaments de denier ultrafin ayant un diamètre de filament moyen allant de 0.05 à 1.8μm, lequel est obtenu en soumettant un non-tissé de fibres ou bande de tissu constitués de filaments à deux composants composés d'une résine thermoplastique hydrosoluble et d'une résine thermoplastique insoluble dans l'eau à dissoudre dans un solvant hydrophile ou à extraction avec un solvant hydrophile de telle façon qu'une partie de la résine thermoplastique hydrosoluble reste dans les fibres ou bande de tissu, où les faisceaux du filament de denier ultrafin ayant une largeur moyenne allant de 3 à 100μm pour 1 à 20% de la surface du non-tissé de fibres et la résistance à la traction dans le sens de la longueur et de la largeur (B) (kgf/5cm) du non-tissé de fibres et le poids de base (A) (g/m2) de celui-ci satisfont à la relation : 100 x (B)/(A) > 5. Le milieu filtrant montre une performance collectrice et une perméabilité aux liquides élevées et est utile en tant que filtre pour des carburants liquides tels que le carburant de moteur diesel.
PCT/JP2007/067969 2006-09-22 2007-09-14 Milieu filtrant et son procédé de fabrication WO2008035637A1 (fr)

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JP2008535339A JPWO2008035637A1 (ja) 2006-09-22 2007-09-14 フィルター材及びその製造方法
EP07807373A EP2065081A4 (fr) 2006-09-22 2007-09-14 Milieu filtrant et son procédé de fabrication
US12/442,124 US20100072126A1 (en) 2006-09-22 2007-09-14 Filter material and method for producing the same

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JP2006256938 2006-09-22
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JP2009287415A (ja) * 2008-05-27 2009-12-10 Unitica Fibers Ltd 自動車燃料フィルター材
JP2011515569A (ja) * 2008-03-28 2011-05-19 スリーエム イノベイティブ プロパティズ カンパニー 粒子の表面改質のための方法
JP2011098326A (ja) * 2009-11-09 2011-05-19 Kitagawa Ind Co Ltd ベントフィルタおよびベントフィルタの製造方法
JP2014158988A (ja) * 2013-02-19 2014-09-04 Kuraray Co Ltd 水処理不織布フィルター
JP2020125756A (ja) * 2014-12-01 2020-08-20 愛三工業株式会社 燃料用フィルタ
WO2023210131A1 (fr) * 2022-04-25 2023-11-02 三菱重工業株式会社 Procédé de production de filtre

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US20040260034A1 (en) 2003-06-19 2004-12-23 Haile William Alston Water-dispersible fibers and fibrous articles
US7892993B2 (en) 2003-06-19 2011-02-22 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
US20080160859A1 (en) * 2007-01-03 2008-07-03 Rakesh Kumar Gupta Nonwovens fabrics produced from multicomponent fibers comprising sulfopolyesters
US8512519B2 (en) * 2009-04-24 2013-08-20 Eastman Chemical Company Sulfopolyesters for paper strength and process
BR112012020099B1 (pt) * 2010-02-12 2021-10-13 Donaldson Company, Inc Filtro para filtrar combustíveis líquidos
US9273417B2 (en) 2010-10-21 2016-03-01 Eastman Chemical Company Wet-Laid process to produce a bound nonwoven article
US20140326661A1 (en) * 2011-08-12 2014-11-06 Donaldson Company, Inc. Liquid filtration media containing melt-blown fibers
US8840758B2 (en) 2012-01-31 2014-09-23 Eastman Chemical Company Processes to produce short cut microfibers
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JP6007851B2 (ja) * 2013-04-08 2016-10-12 日立金属株式会社 絶縁電線、およびそれを用いたコイル、モータ
US9617685B2 (en) 2013-04-19 2017-04-11 Eastman Chemical Company Process for making paper and nonwoven articles comprising synthetic microfiber binders
US9605126B2 (en) 2013-12-17 2017-03-28 Eastman Chemical Company Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion
US9598802B2 (en) 2013-12-17 2017-03-21 Eastman Chemical Company Ultrafiltration process for producing a sulfopolyester concentrate
CN111797498A (zh) * 2020-05-29 2020-10-20 东南大学 一种用于rto的低维度器件群的设计方法
CN113308797B (zh) * 2021-05-08 2023-02-07 安丹达工业技术(上海)有限公司 熔喷布及其制法和含有其的口罩和空气过滤装置

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Publication number Priority date Publication date Assignee Title
JP2011515569A (ja) * 2008-03-28 2011-05-19 スリーエム イノベイティブ プロパティズ カンパニー 粒子の表面改質のための方法
JP2016065237A (ja) * 2008-03-28 2016-04-28 スリーエム イノベイティブ プロパティズ カンパニー 粒子の表面改質のための方法
JP2009287415A (ja) * 2008-05-27 2009-12-10 Unitica Fibers Ltd 自動車燃料フィルター材
JP2011098326A (ja) * 2009-11-09 2011-05-19 Kitagawa Ind Co Ltd ベントフィルタおよびベントフィルタの製造方法
JP2014158988A (ja) * 2013-02-19 2014-09-04 Kuraray Co Ltd 水処理不織布フィルター
JP2020125756A (ja) * 2014-12-01 2020-08-20 愛三工業株式会社 燃料用フィルタ
JP7098682B2 (ja) 2014-12-01 2022-07-11 愛三工業株式会社 燃料用フィルタ
WO2023210131A1 (fr) * 2022-04-25 2023-11-02 三菱重工業株式会社 Procédé de production de filtre

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KR20090057454A (ko) 2009-06-05
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EP2065081A4 (fr) 2011-02-23
TW200824779A (en) 2008-06-16

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